Terpene ethers



Patented Mar. 18, 1947 TERPENE ETHERS Richard F. B. Cox, Wilmington, Del., assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application October 4, 1943, Serial No. 504,927

4 Claims. (Cl. 260-611) This invention relates to new terpene compounds and a method for their formation. More particularly, it refers to new ethers of terpenes and nitro-suhstituted monohydroxy alcohols and to a method for their preparation.

By the method in accordance with this invention, a terpene compound is brought into intimate contact with a nitro-containing monohydric al cohol and is reacted therewith until a nitro-containing terpene ether is formed.

More particularly, by the method of this invention, a terpene compound as, for example, camphene or pinene is brought into intimate contact with a intro-containing monohydric primary alcohol and heated in the presence of a suitable catalyst as, for example, phosphoric acid until a nitro-containing terpene ether is formed.

The method in accordance with this invention is illustrated by the following specific examples. All parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 Z-meihyZ-Z-nizropropyl isobornyl ether A mixture of 360 g. of camphene, 2'75 g. of nitroisobutyl alcohol, and 100 g. of 85% phosphoric acid were heated at a temperature between 3040 C. for one hour with vigorous stirring. After standing for 16 hours at room temperature, the

EXAMPLE 2 p-Nitrobeneyl isobomyl ether EXAMPLE 3 Z-m'troisoamyl isobornyl ether A mixture of 290 g. camphene, 150 g. of nitroisoamyl alcohol and g. of phosphoric acid was stirred at 30-44? C. for 24 hours and was then poured into water and extracted with ml. benzene. The benzene extract was washed free of phosphoric acid with 5% sodium bicarbonate solution. After removal of the benzene under re duced pressure, there remained 270 g. oily isoloornyl ether of 2-nitroisoamyl alcohol.

Each of the following examples was carried out in the manner set forth in Example 1:

Reaction Nitro concondltlons taining Ex. Terpene, parts Nitro compound Parts Catalyst Parts terpene ether Time Temp. parts Hours 0. 4 Allo-oclmene 136 Nitroethanol 100 85% H POrm- 80 48 30 5 Pinene 180 2-methyl-2-n1tro propyl alcohol 85% H3P04.. 60 42 340 193 mixture was re-heated to a temperature of between about 30-40 C. for 25 hours whereupon two layers of liquid were formed, the upper layer containing the product. About 200 ml. of benzene Were added to the mixture which was then washed several times with water followed by two washings with. dilute sodium hydroxide solution. A few sodium hydroxide pellets were added to the water-Washed mixture and the solution then steam distilled for 3 /2 hours to remove the benzene and unreacted camphene. The oily product was dissolved in 500 cc. of petroleum ether and water washed several times to removeany sodium hydroxide present. After removal of the petroleum ether by heating under reduced pressure, 381 g. of 2-methyl-2-nitropropyl camphene ether were obtained. Analysis showed 5.5% nitrogen.

In accordance with this invention, a nitro-containing terpene ether may be formed from a terpene and a nitro-containing monohydric alcohol. Nitro-containing compounds suitable for the preparation of these ethers are nitrosubstituted monohydric alcohols. These alcohols may be aliphatic or aromatic. Primary monohydric nitrosubstituted alcohols are preferred. Suitable mon-- groups containing elements such as oxygen, sulfur, nitrogen, halogen,'etc. Suitable unsaturated terpenes which may be utilized are such unsaturated terpene hydrocarbons as, for example, al-

pha-pinene, beta-pinene, sylvestrene, alpha-ter-f pineol, beta-terpineol, terpinenol, or unsaturated complex cyclic terpenes capable of isomerization to unsaturated monocyclic terpene compounds such as alpha-pinene, beta-pinene, sabinene,

carene; or cyclic terpenes, which are not readily V isomerized to monocyclic terpenes such as fenchene, camphene, and bornylene, may be employed. The terpene compounds need not be in the form of pure compounds for the purpose of the preparation of the ether, but maybe used in the form of crude natural mixtures of terpene compounds as, for example, turpentine, pine oil, etc. Each of the terpenes listed will react under conditions like or similar to those given in the examples.

With some of the terpenes a mixture of products is obtained. For example, with camphene as a starting material, the chief product is'an iso bornyl ether but a small amount of bornyl ether may also be obtained; with pinene as a starting material, the main product is a terpinyl ether but a small amount of other terpene ethers, such as ethers of borneol, isoborneol, terpinenel-ol and beta-terpineol, is alsoobtained.

The reaction is brought about by mixing the terpenes and the intro-containing compounds preferably in "alcohol in the presence of a suitable catalyst as, for example, acid catalysts such as phosphoric acid in 85% concentration, 25-50% sulfuric acid, p-toluenesulfonic acid, hydrofluoric acid, and boron halides, such as boron trifiuoride and boron trifiuoride-ether complex.

Tre reaction may be conducted at any temperature in the range between about C-. to about 130 C. and preferably between about40 C. and about 50 C; Under exothermic reaction conditions, it is desirable to provide external cooling means for maintaining the reaction conditions at the desired temperature. The specific reaction temperature will be dependent upon the catalyst used. For example, temperatures from' 80 C.-130 C. are suitable when paratoluenesulfonic acid is used. When hydrofluoric acid or boron trifiuoride is used as the catalyst, temperatures of 0 C.30 C. are most suitable While a temperature range of about 30 C. to about 80 C. is preferred when the catalyst is phosphoric acid or dilute sulfuric acid.

The time required to form nitro-containing terpene ethers by the method in accordance with Usually, the liquid reaction mixture will consist essentially of the terpenes and the nitrocontaining alcohol reactant, with the alcohol in excess of that expected to enter into the reaction. However, inert diluents such as benzene, toluene, chloroform, petroleum ether, and the like, may be added.

The etherification reaction in, accordance with 7 ,this invention produces a nitro-containing terpene ether of the following general formulaz 'NO2ROT, where Rrepresents a bivalent.

hydrocarbon radical from a monohydric alcohol,

. preferably from an aliphatic or aromatic primary monohydric alcohol, and T represents a terpene radical. The rate of etherification may be controlled by adjusting the conditions of reaction as, for example, time, temperature, proportion or reactant and/or catalyst. The reaction may be conducted in the substantial absence of or in the presence of a small amount of water. Large quantities of water tend to slow down the reaction due to the increased immiscibilitywith the terpene. Hence, where water is utilized, the

quantity will preferably be in the range between a minor quantity such'as 5% of the nitrohydric compound up to about the quantity of the nitrohydric compound by molecular proportion.

The nitro-containing terpene ethers made in accordance with this invention are useful either in a suitable carrier as, for example, deodorized kerosene, with 2.5% pyrethrum, (20:1 COIlCGl'l-r tration) the results of toxicity show an increase over the toxicity of either one of the components when used alone under like conditions.

From the foregoing description, it is apparent that a new product and method of production has been provided. More specifically, a nitrocontaining terpene ether of a monohyd-ric organic compound has been provided having insecticidal activating properties;

' This application is a continuation-in-part of my application, for UnitedStates Letters Patent, Serial No. 452,499, filed July 27, 1942.

What I claim and desire to protect by Letters Patent is: N

1. An ether of a terpene and a nitro-substituted monohydric alcohol selected from the group consisting of nitroethanol, propyl alcohol, and nitroisoamyl alcohol.

2. An ether of 2-'i'ne-t hyl-2-nitropropyl alcohol and a terpene.

3. An ether of 2-methyl-2-nitropropyl alcohol and camphene.

4. 2-methyl-2-nitropropyl isobornyl ether.

RICHARD F. B. COX;

, ananaenons crrEn The following references are. of record in file of this patent:

UNITED STATES PATENTS Name I I Date Humphrey M'ar..28, l 939 the Number 2-methyl-2-nitro- 

